Thermally or photochemically induced reductive cleavage of metal-metal bonds of metal carbonyl dimers by a titanocene(III) tert-butoxide: Novel reversible access to heterobimetallic complexes

Kouki Matsubara, Shota Niibayashi, Hideo Nagashima

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15 Citations (Scopus)

Abstract

Novel synthetic methods for Ti Mo, Ti-W, and Ti-Ru heterobimetallic complexes are established by the reaction of a certain titanium(III) alkoxide and the corresponding metal carbonyl dimer, [CpM(CO)n]2 [M = Mo, W (n = 3); M = Ru (n = 2)]. Thus, a novel monomeric titanium complex, Cp2Ti(OtBu) (1), which is synthesized from Cp2TiCl and KOtBu and characterized by spectroscopy and crystallography, smoothly reacts with [CpM(CO)3]2 (M = Mo (2a), W (2b)) to give heterobimetallic complexes, Cp2Ti(OtBu)(u-OC)M(CO)2Cp (M = Mo (3a) and W (3b)), of which two metallic moieties are linked by the isocarbonyl bridge. Similar reaction of 1 with [CpRu(CO)2]2 (4) does not occur thermally, but is accomplished under photoirradiation to afford Cp2(OtBu)Ti-Ru(CO)2Cp (5), of which two metallic moieties are linked by a direct metal-metal bond. Use of 1 is particularly important for these reactions; other titanium alkoxides such as [Cp2Ti(OMe)]2 and Cp2Ti[O(2,6-tBu2-4-Me)C6H2] do not react with the metal carbonyl dimers. An interesting feature of these new heterobimetallic complexes, 3a, 3b, and 5, is the existence of the thermal fragmentation process to regenerate the starting materials: 3a or 3b is actually in equilibrium with a mixture of 1 and 2a or 1 and 2b, respectively [ΔG298k0 = -4.1 ± 0.2 kcal mol-1 (3a), -4.3 ± 0.2 kcal mol-1 (3b)]. The Ti-Ru compound 5 thermally undergoes fragmentation to regenerate 1 and 4. The formation of these heterobimetallic complexes is formally considered as the metal-metal bond cleavage of metal carbonyl dimers by a Ti(III) reducing reagent; possible mechanisms are discussed.

Original languageEnglish
Pages (from-to)1376-1382
Number of pages7
JournalOrganometallics
Volume22
Issue number7
DOIs
Publication statusPublished - Mar 31 2003

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Dimers
cleavage
Metals
dimers
Carbon Monoxide
metals
Titanium
titanium
alkoxides
fragmentation
Crystallography
titanocene
crystallography
reagents
Spectroscopy
spectroscopy

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

@article{79cd8b24044d4da39e88b4889eb0a1b8,
title = "Thermally or photochemically induced reductive cleavage of metal-metal bonds of metal carbonyl dimers by a titanocene(III) tert-butoxide: Novel reversible access to heterobimetallic complexes",
abstract = "Novel synthetic methods for Ti Mo, Ti-W, and Ti-Ru heterobimetallic complexes are established by the reaction of a certain titanium(III) alkoxide and the corresponding metal carbonyl dimer, [CpM(CO)n]2 [M = Mo, W (n = 3); M = Ru (n = 2)]. Thus, a novel monomeric titanium complex, Cp2Ti(OtBu) (1), which is synthesized from Cp2TiCl and KOtBu and characterized by spectroscopy and crystallography, smoothly reacts with [CpM(CO)3]2 (M = Mo (2a), W (2b)) to give heterobimetallic complexes, Cp2Ti(OtBu)(u-OC)M(CO)2Cp (M = Mo (3a) and W (3b)), of which two metallic moieties are linked by the isocarbonyl bridge. Similar reaction of 1 with [CpRu(CO)2]2 (4) does not occur thermally, but is accomplished under photoirradiation to afford Cp2(OtBu)Ti-Ru(CO)2Cp (5), of which two metallic moieties are linked by a direct metal-metal bond. Use of 1 is particularly important for these reactions; other titanium alkoxides such as [Cp2Ti(OMe)]2 and Cp2Ti[O(2,6-tBu2-4-Me)C6H2] do not react with the metal carbonyl dimers. An interesting feature of these new heterobimetallic complexes, 3a, 3b, and 5, is the existence of the thermal fragmentation process to regenerate the starting materials: 3a or 3b is actually in equilibrium with a mixture of 1 and 2a or 1 and 2b, respectively [ΔG298k0 = -4.1 ± 0.2 kcal mol-1 (3a), -4.3 ± 0.2 kcal mol-1 (3b)]. The Ti-Ru compound 5 thermally undergoes fragmentation to regenerate 1 and 4. The formation of these heterobimetallic complexes is formally considered as the metal-metal bond cleavage of metal carbonyl dimers by a Ti(III) reducing reagent; possible mechanisms are discussed.",
author = "Kouki Matsubara and Shota Niibayashi and Hideo Nagashima",
year = "2003",
month = "3",
day = "31",
doi = "10.1021/om020869l",
language = "English",
volume = "22",
pages = "1376--1382",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "7",

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TY - JOUR

T1 - Thermally or photochemically induced reductive cleavage of metal-metal bonds of metal carbonyl dimers by a titanocene(III) tert-butoxide

T2 - Novel reversible access to heterobimetallic complexes

AU - Matsubara, Kouki

AU - Niibayashi, Shota

AU - Nagashima, Hideo

PY - 2003/3/31

Y1 - 2003/3/31

N2 - Novel synthetic methods for Ti Mo, Ti-W, and Ti-Ru heterobimetallic complexes are established by the reaction of a certain titanium(III) alkoxide and the corresponding metal carbonyl dimer, [CpM(CO)n]2 [M = Mo, W (n = 3); M = Ru (n = 2)]. Thus, a novel monomeric titanium complex, Cp2Ti(OtBu) (1), which is synthesized from Cp2TiCl and KOtBu and characterized by spectroscopy and crystallography, smoothly reacts with [CpM(CO)3]2 (M = Mo (2a), W (2b)) to give heterobimetallic complexes, Cp2Ti(OtBu)(u-OC)M(CO)2Cp (M = Mo (3a) and W (3b)), of which two metallic moieties are linked by the isocarbonyl bridge. Similar reaction of 1 with [CpRu(CO)2]2 (4) does not occur thermally, but is accomplished under photoirradiation to afford Cp2(OtBu)Ti-Ru(CO)2Cp (5), of which two metallic moieties are linked by a direct metal-metal bond. Use of 1 is particularly important for these reactions; other titanium alkoxides such as [Cp2Ti(OMe)]2 and Cp2Ti[O(2,6-tBu2-4-Me)C6H2] do not react with the metal carbonyl dimers. An interesting feature of these new heterobimetallic complexes, 3a, 3b, and 5, is the existence of the thermal fragmentation process to regenerate the starting materials: 3a or 3b is actually in equilibrium with a mixture of 1 and 2a or 1 and 2b, respectively [ΔG298k0 = -4.1 ± 0.2 kcal mol-1 (3a), -4.3 ± 0.2 kcal mol-1 (3b)]. The Ti-Ru compound 5 thermally undergoes fragmentation to regenerate 1 and 4. The formation of these heterobimetallic complexes is formally considered as the metal-metal bond cleavage of metal carbonyl dimers by a Ti(III) reducing reagent; possible mechanisms are discussed.

AB - Novel synthetic methods for Ti Mo, Ti-W, and Ti-Ru heterobimetallic complexes are established by the reaction of a certain titanium(III) alkoxide and the corresponding metal carbonyl dimer, [CpM(CO)n]2 [M = Mo, W (n = 3); M = Ru (n = 2)]. Thus, a novel monomeric titanium complex, Cp2Ti(OtBu) (1), which is synthesized from Cp2TiCl and KOtBu and characterized by spectroscopy and crystallography, smoothly reacts with [CpM(CO)3]2 (M = Mo (2a), W (2b)) to give heterobimetallic complexes, Cp2Ti(OtBu)(u-OC)M(CO)2Cp (M = Mo (3a) and W (3b)), of which two metallic moieties are linked by the isocarbonyl bridge. Similar reaction of 1 with [CpRu(CO)2]2 (4) does not occur thermally, but is accomplished under photoirradiation to afford Cp2(OtBu)Ti-Ru(CO)2Cp (5), of which two metallic moieties are linked by a direct metal-metal bond. Use of 1 is particularly important for these reactions; other titanium alkoxides such as [Cp2Ti(OMe)]2 and Cp2Ti[O(2,6-tBu2-4-Me)C6H2] do not react with the metal carbonyl dimers. An interesting feature of these new heterobimetallic complexes, 3a, 3b, and 5, is the existence of the thermal fragmentation process to regenerate the starting materials: 3a or 3b is actually in equilibrium with a mixture of 1 and 2a or 1 and 2b, respectively [ΔG298k0 = -4.1 ± 0.2 kcal mol-1 (3a), -4.3 ± 0.2 kcal mol-1 (3b)]. The Ti-Ru compound 5 thermally undergoes fragmentation to regenerate 1 and 4. The formation of these heterobimetallic complexes is formally considered as the metal-metal bond cleavage of metal carbonyl dimers by a Ti(III) reducing reagent; possible mechanisms are discussed.

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